The present invention relates to the field of compositions of polymerisable monomers which, after polymerisation, give transparent polymer substrates, and to their use for making optical, particularly ophthalmic, lenses.
Optical lenses for ophthalmic use made from organic polymer materials are known and have been used for many years.
One of the most widely used materials is obtained by polymerization of compositions containing diethylene glycol diallyl carbonate (subsequently referred to as CAD).
This monomer is commercially available, for example under the trade name CR39(copyright).
An example of a commercial ophthalmic lens in a material of this type is the ORMA(copyright) lens.
This material has intrinsically good mechanical properties, in particular impact strength and scratch resistance, as well as good resistance to organic solvents.
This material may also be readily coloured when desired by the customer.
One of the disadvantages of the use of CAD is the fact that the polymerisation of this monomer is essentially performed thermally, with particularly long heat cycles (several hours or even days).
It would thus be desirable to reduce the length of these polymerisation cycles so as, amongst other reasons, to be able to respond to customers as quickly as possible, to limit the length of time that the moulds used for the lens production are in use, and to reduce the manufacturing costs.
In addition, although CAD materials are generally satisfactory, it would also be desirable to produce materials with improved intrinsic properties.
Various types of materials have already been proposed in the prior art.
The patent U.S. Pat. No. 4,138,538 discloses compositions of allyl monomers such as CAD, containing a methacrylic monomer such as a polyethylene glycol di(meth)acrylate.
This methacrylic monomer may be used at a concentration of 20 to 70% by weight of the polymerisable mixture.
The mixture is photopolymerised, preferably at low temperature, then a thermal treatment is performed.
The patent U.S. Pat. No. 4,650,845 discloses monomer compositions comprising from 0 to 100 parts by weight of a first component which is a poly(meth)acrylate urethane monomer, and from 100 to 0 parts by weight of a second component which is a composition containing:
A) from 30 to 60% by weight of a polyacrylate monomer,
B) from 20 to 70% by weight of a modifier of the shrinkage during the polymerisation,
C) from 0 to 30% by weight of a diluent monomer.
The compositions are preferably photopolymerised.
In practice, the compositions disclosed generally lead to highly crosslinked polymers due to the presence of monomers containing multiple functional groups.
The compositions generally contain monomers containing at least 4 (meth)acrylate groups.
The patent U.S. Pat. No. 4,912,185 discloses compositions of polymerisable monomers, for the production of ophthalmic lenses or video discs, comprising at least one polyoxyalkylene glycol acrylate or methacrylate monomer, at least one crosslinking agent containing several unsaturated functions and at least one urethane monomer with 2 to 6 methacrylic end groups.
In practice, the crosslinking agent cited above contains 3 to 4 vinyl, acrylic or methacrylic functional groups.
Such compositions are preferably hardened by mixed UV/thermal polymerisation.
The patent EP-A-453149 discloses compositions containing a polyoxyalkylene glycol di(meth)acrylate monomer, a monomer containing a bisphenol A unit and leading, by homopolymerisation, to a polymer with refractive index greater than 1.55 and a urethane monomer with 2 to 6 (meth)acrylic end groups.
The polymerisation is preferably mixed UV/thermal.
The patent U.S. Pat. No. 5,183,870 discloses compositions comprising from 10 to 60% by weight of a polybutylene glycol di(meth)acrylate, from 20 to 80% by weight of a poly(meth)acrylate urethane, from 5 to 60% by weight of a specific mono(meth)acrylate monomer and from 0 to 60% by weight of a compound having at least one polymerisable double bond.
According to the patent U.S. Pat. No. 5,183,870, the choice of the polybutylene glycol di(meth)acrylate is essential to achieve a good compromise between impact strength and low water absorption properties.
Comparative example 7 discloses a composition containing a polyethylene glycol di(meth)acrylate, a dimethacrylate urethane and a tricyclo[5.2.1.02,6]decan-8-yl methacrylate.
The polymer resulting from this composition has a high water absorption level of 3.6%.
The patent U.S. Pat. No. 5,880,171 discloses photopolymerisable compositions containing:
from 20 to 90%, and preferably at least 50% by weight of an epoxy or polyester urethane oligomer with (meth)acrylate end groups and 5 to 80% by weight of an optional diluent which is a hydrocarbon diol ester with (meth)acrylate and/or tri, tetra or poly(meth)acrylate end groups.
The patent U.S. Pat. No. 5,566,027 discloses photopolymerisable compositions comprising from 25 to 45% of a polyester urethane oligomer containing several (meth)acrylic groups linked to a polyester oligomer via a urethane group and having a molecular weight of at least 700, from 31 to 70% by weight of a polyfunctional (meth)acrylate with an average molecular weight of at least 700 and from 5 to 55% by weight of a monofunctional (meth)acrylate.
This composition is used as a varnish applied to ophthalmic lenses.
There is no provision for the use of a composition of this type to produce the body of the lens.
Thus it can be seen that many polymerisable compositions leading to materials with refractive index of the order of 1.5 have been proposed in the prior art, without however giving complete satisfaction for producing transparent polymer substrates usable in the optics field.
A first object of the present invention is thus to provide new compositions of polymerisable monomers leading to transparent polymer substrates able to be substituted for CAD-based polymers, in other words with properties which are overall similar to those of CAD, and preferably better.
The optical substrates must in particular have all the following properties:
high transparency (transmission generally greater than 85%, and preferably greater than or equal to 90%), with an absence of, or only very slight, diffusion of the light,
low density, less than 1.4, preferably less than 1.3 and even better less than 1.2,
refractive index between 1.48 and 1.52,
high Abbe number, greater than or equal to 40, preferably greater than or equal to 45 and even better greater than or equal to 50, so as to avoid chromatic aberrations,
absence of colour after polymerisation, in particular a low yellow index and an absence of yellowing over time,
good impact strength (in particular an uncoated lens should preferably pass the FDA ball dropping test),
good resistance to static stresses,
good scratch resistance,
good suitability for accepting different treatments (deposit of hard, anti-reflection, primary anti-shock coatings, etc.), and particular good suitability for coloration,
good suitability for surface and edge finishing treatments, without the overall geometry of the lens being distorted during such operations,
low water absorption level.
The polymer substrates according to the invention have a water absorption level which is preferably less than 1.5% and more preferably less than 1%.
A second object of the invention is to provide compositions which may be readily and rapidly polymerised, in particular by photopolymerisation or by mixed photo- and thermal polymerisation techniques, so as to reduce the length of the lens production cycle.
The composition of the polymerisable monomers according to the invention comprises:
40 to 95 parts by weight of one or more monomers (I) of formula: 
in which
R1 and R2 represent H or CH3,
A represents a divalent radical of formula 
m1 and m2 are each integers varying from 2 to 6, and
5 to 50 parts by weight of a monomer (II) comprising at least one urethane unit and at least two (meth)acrylate functions.
The composition of monomers according to the invention generally has a viscosity less than or equal to 0.3 Pa.s, preferably less than 0.2 Pa.s.
The first important component of the compositions according to the invention is the monomer or monomers (I) corresponding to the formula above.
More exactly, it consists of (meth)acrylic esters of propylene glycol containing a central radical A, which may be linear or branched, such as defined above.
The first component is a monomer or mixture of monomers (I) with relatively short chain lengths, in other words the number of propylene glycol units present in the radical A must be equal to or less than 6 and preferably between 2 and 6 for each of the monomers (I).
When several monomers (I) are used in a mixture, an average value may be defined:       m    _    =            ∑              m        =        2            6        ⁢          xe2x80x83        ⁢                  X        m            ·      m      
in which Xm is the ratio by weight of monomer (I) for which A contains m propylene glycol units in its chain compared to the total weight of monomers of formula (I).
When commercially available products which are already mixtures of monomers are used as the first component of the invention, this value {overscore (m)} may easily be obtained by HPLC analysis of the mixture followed by the calculation   Xm  =      Sm          S      ⁢              xe2x80x83            ⁢      total      
where Sm represents the area of the peak corresponding to the monomer (I) containing m propylene glycol units in the divalent radical A, and S represents the total area of all the peaks corresponding to the monomers (I) for which m varies from 2 to 6.
According to the invention, it is preferable to use mixtures of several monomers (I) whose average value {overscore (m)} as defined above is less than 5 and preferably varies from 2 to 4.
It is also preferable that the monomers (I) have a branched structure, in other words that the radical A represents: 
m2 having the meaning stated previously.
The compositions according to the invention comprise from 50 to 95 parts by weight of monomer (I), the total weight of monomers (I) and (II) representing 100 parts by weight.
It is preferable to use a mixture of several monomers (I) whose central unit A is: 
with m2 being an integer with value from 2 to 6 according to the following mass ratios:
m2=2 27%
m2=3 47%
m2=4 20%
m2=5 4%
m2=6 2%
with an average value {overscore (m)}2=3.07.
This mixture will be referred to in the remainder of this application as PPG 200 di(meth)acrylate (or PPG 200 DMA).
In general the first component contributes rigidity to the polymer network comprising the final substrate.
The second component of the compositions according to the invention is a monomer or mixture of monomers (II) comprising at least one urethane unit and at least two (meth)acrylate functions.
Two families of monomers (II) with urethane units are preferably used.
The first family consists of urethane di(meth)acrylate oligomers, and, preferably, those which are aliphatic polyesters.
Examples of such compounds are the urethane di(meth)acrylate oligomers from the company Cray Valley, in particular the product known under the trade name CN934(copyright).
The second family consists of monomers (II) with the formula 
in which Q is a radical of valency n, with linear, branched or cyclic structure, containing at least two units of formula: 
W is a divalent alkyl radical, with linear or branched structure, with from 1 to 5 carbon atoms.
n varies from 2 to 4
R represents H or CH3xe2x80x94, and
Rxe2x80x2 represents H or a valence bond
W preferably represents the radical xe2x80x94CH2CH2xe2x80x94
Q preferably represents a divalent radical of formula: 
in which X represents a linear or branched divalent alkyl chain with from 1 to 15 carbon atoms, preferably 8 to 12 carbon atoms.
Rxe2x80x21 and Rxe2x80x22 independently represent H or CH3.
A monomer of this type is commercially available under the trade name PLEX(copyright) 6661-0 and has the formula: 
in which Rxe2x80x23 and Rxe2x80x24 independently represent H or CH3.
Among the second family of monomers (II), other preferred monomers are those in which Q represents a trivalent radical of formula: 
Monomers of this type which are commercially available have the formula: 
in which Rxe2x80x31, Rxe2x80x32 and Rxe2x80x33 independently represent H or CH3.
The monomer of the above formula in which Rxe2x80x31, Rxe2x80x32 and Rxe2x80x33 each represent a methyl group is available from the company Cray Valley under the trade name SR290.
The monomer of the above formula in which Rxe2x80x31, Rxe2x80x32 and Rxe2x80x33 each represent a hydrogen atom is available from the company Cray Valley under the trade name SR368.
The monomer (II) is present in a proportion of 5 to 50 parts by weight, preferably 10 to 40 parts by weight compared to the total weight of monomers (I) and (II).
Commercially available monomers include:
1. aliphatic diacrylate urethanes
CN934, 964, 965, 963, 966, 967, 981 from the company Cray Valley;
EBECRYL 230, 244, 245, 270, 284, 285, 4830, 4835, 8800 from the company UCB;
2. aromatic diacrylate urethanes
CN970, 972, 973 and 976 from the company Cray Valley;
EBECRYL 210, 215, 4244 from the company UCB;
3. urethane acrylates with functionality xe2x89xa73
Triacrylate: CN920, 922, 923, 924, 929 (Cray Valley) EBECRYL 204, 205, 254, 264, 265 (UCB)
Tetracrylate : CN925, 945, 995 (Cray Valley) U4HA (SHIN NAKAMURA)
Hexaacrylate: CN975 (Cray Valley) EBECRYL 220,1290, 2220, 5129 (UCB); U6HA (SHINNAKAMURA)
4. aliphatic methacrylate urethanes
PLEX(copyright) 66610 (ROHM);
U4H (tetrafunctional methacrylate from SHIN NAKAMURA).
The monomer compositions according to the invention may include other polymerisable monomers (III) different from monomers (I) and (II), which may integrate into the final network obtained, in particular monomers polymerisable by free radical mechanisms.
These monomers (III) represent from 0 to 30%, preferably 0 to 10% by weight, compared to the total weight of monomers (I) and (II).
These monomers (III) may include the alkyl (meth)acrylates such as methyl (meth)acrylate and ethyl (meth)acrylate, the cycloallkyl (meth)acrylates such as cyclohexyl (meth)acrylate and dicyclopentyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, the naphthyl (meth)acrylates, the phenoxyalkyl (meth)acrylates such as phenoxyethyl (meth)acrylate and phenoxybutyl (meth)acrylate, the alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate, the poly(alkylene) glycol di(meth)acrylates different from the monomers (I) such as poly(ethylene) and poly(butylene) glycol di(meth)acrylates, neopentyl glycol di(meth)acrylate, compounds of bisphenol-A di(meth)acrylates and their mixtures.
The compounds of bisphenol-A di(meth)acrylates include compounds of formula: 
in which R5 represents H or CH3 and n1+n2 has an average value of from 0 to 40.
Preferred compounds corresponding to the above formula are those for which R5=CH3 and {overscore (n1+n)}2=2.6 (EBADMA), {overscore (n1+n)}2=4 (DBADMA), {overscore (n1+n)}2=10 (OBADMA) and {overscore (n1+n)}2=30.
The monomer (III) may be one monomer or a mixture of monomers corresponding to the chemical structure of monomer (I) and for which m1 or m2 is an integer greater than 6, generally from 7 to 20. In this case, the quantity of monomers (III) is such that the mean:       m    _    =            ∑              m        =        1            20        ⁢          xe2x80x83        ⁢                  X        m            ·      m      
remains less than 5.
The additional monomer (III) may be a monomer with high Abbe number and containing one or more (meth)acrylate functions.
By monomer with high Abbe number should be understood a monomer able to generate, by homopolymerisation, a transparent polymer with high Abbe number, in other words at least 50, and preferably at least 55.
The monomer with high Abbe number preferably contains at least one non-aromatic cyclic or polycyclic hydrocarbon radical.
The monomer (III) with high Abbe number is preferably selected from at least one of the monomers of the following formula: 
In these formulas:
Y is a divalent radical selected from xe2x80x94Oxe2x80x94, xe2x80x94CH2xe2x80x94, xe2x80x94C(CH3)2xe2x80x94, xe2x80x94C(H)(CH3)
Z is a divalent radical selected from xe2x80x94(CH2)pxe2x80x94Oxe2x80x94
p being an integer from 1 to 4, and 
Ra, Rb represent H or CH3 
Rc, Rd independently represent a linear or branched alkyl radical with 1 to 6 carbon atoms
Ri, Rj independently represent a linear or branched alkyl radical with 1 to 10 carbon atoms
w is an integer from 1 to 3,
x is an integer from 0 to 3,
y is an integer from 0 to 3,
on condition that x+yxe2x89xa71,
k is an integer from 0 to 6.
l is an integer from 0 to 6,
r is an integer from 0 to 6,
s is an integer from 0 to 6,
z is an integer from 0 to 3, and
t is an integer from 0 to 3.
The monomers (III) with high Abbe number which are particularly preferred are selected from the monomers of formula: 
The compositions according to the invention also contain a system for initiating the polymerisation. The system for initiating the polymerisation may comprise one or more agents for initiating thermal or photochemical polymerisation or a mixture of thermal and photochemical initiation agents. These initiators are well known in the state of the art and any conventional initiator may be used. The thermal polymerisation initiators which may be used in the present invention include the peroxides such as benzoyl peroxide, cyclohexyl peroxydicarbonate, and isopropyl peroxydicarbonate.
The photoinitiators include in particular 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, and the alkyl benzoyl ethers.
The initiators are in general used in a proportion of 0.01 to 5% by weight compared to the total weight of polymerisable monomers in the composition.
The polymerisable compositions according to the invention may also contain additives conventionally used in polymerisable compositions for moulding optical or ophthalmic articles, in particular spectacle glasses and lenses, in conventional proportions, for example inhibitors, colorants, UV absorbers, perfumes, deodorants, antioxidants, anti-yellowing agents and photochromic compounds.
The compositions according to the invention may be polymerised thermally, photochemically or by a combination of the two methods.